GB2104090A

GB2104090A - Triazine compounds

Info

Publication number: GB2104090A
Application number: GB08218108A
Authority: GB
Inventors: Willy Stingelin; Visvanathan Ramanathan
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1981-06-26
Filing date: 1982-06-22
Publication date: 1983-03-02
Also published as: GB2104090B; CH650011A5; DE3223436A1

Abstract

There are described novel basic and cationic triazine compounds of the formulae I and Ia <IMAGE> or mixtures thereof, wherein the symbols have the meanings defined in Claim 1, and also the production of these compounds. The novel compounds are very suitable in particular for dying paper, and yellow to blue dyeings having fastness to water are obtained. wherein A, B and C independently of one another are each a group of the formula II <IMAGE> or one of the groups A, B or C is a group of the formula III -NHX and the other two independently of one another correspond to the formula in which formulae, the phenylene group D can be substituted, K is any chosen coupling component, X is an unsubstituted or substituted C1-5-alkyl group, Y is a basic group, and Y1 is a quaternary group, n is the number 2, 3 or 4, and An is any given anion.

Description

SPECIFICATION Triazine compounds The invention relates to novel triazine compounds, to processes for producing them, and to their use as dyes for dyeing and printing textile materials, leather and in particular paper.

The novel triazine compounds are basic compounds of the formula I or cationic compound of the formula la

or they are mixtures of basic compounds of the formula I with cationic compounds of the formula la. In these formulae, A, B and C independently of one another are each a group of the formula II

wherein the phenylene group D can be substituted, and K is any chosen coupling component, or one of the groups A, B or C corresponds to the formula Ill -NHX (Ill) wherein X is an unsubstituted or substituted C1-C5-alkyl group, and the other two independently of one another correspond to the formula II. Y in the formula I is a basic group, and Y1 in the formula la is a quaternary group; and the symbol n is the number 2, 3 or 4, and An is an anion.

Preferred triazine compounds correspond to the formula la wherein at least two, and in particular 3, of the A, B and C groups are identical and correspond to the formula II.

As a coupling component, K can be for example: acetoacetic acid anilide, phenol, pyridone, quinolone, pyrazolone, aminopyrazole, indole, aniline, aminopyridine, naphthol, naphtholcarboxylic acid anilide, naphthylamine, aminothiazole and thiophene. These groups can be also substituted by for example: a C1-C4-alkyl group (-CH3,-C2H5, n-C3H7, iso-C3H7,-CH2NH2, -C2H4OH or -C2H4Cl), a C1-C4-alkoxy group (-OCH3, -0C2H5, n--OC,H,, iso-0C3H7, -OCH2H4OH or -OC2H4Cl), halogen (F, Cl or Br), NO2, OH and/or CN.

Preferred coupling components are: an acetoacetic acid anilide group, for example of the formula:

a pyridone group, for example of the formula

a naphthol group, for example of the formula

a naphthylamine group, for example of the formula

and a phenol group, for example of the formula

When the phenylene group D is further substituted, suitable substituents are for example: a straight-chain or branched-chain C1-C4-alkyl group, such as the methyl, ethyl n- or iso-propyi group, or the n-, sec- or tert-butyl group; a straight-chain or branched-chain C1-C4-alkoxy group, such as the methoxy, ethoxy, n- and iso-propoxy group, or the n- and iso-butoxy group; halogen, such as fluorine, chlorine or bromine; the CN group, the NO2 group, or an S02-alkyl(C1-C4) group, such as the methylsulfonyl or ethylsulfonyl group or the n- or iso-propylsulfonyl group. In the preferred triazine compounds, the phenylene ring D is either not further substituted or further substituted by a C1-C4-alkyl group or a C1-C4-alkoxy group.

As a C1-C5-alkyl group, X is for example a straight-chain or branched-chain alkyl group, for example a methyl, ethyl, n- or iso-propyl group, n- or iso-butyl group, or n- or iso-pentyl group. These alkyl groups X can be substituted for example by the OH group, by halogen, such as fluorine, chlorine or bromine, by a straight-chain or branched-chain C1-C4-alkoxy group, or by an acylamino group, such as the acetylamino group, or the benzoylamino group. These acyl groups can then for their part be further substituted for example by halogen, such as fluorine, chlorine or bromine, or by an amino group which is mono- or disubstituted on the N atom by for example C1-C4-alkyl.

As a basic group, Y is in particular an amino group of the formula

wherein R5 and R6 independently of one another are: hydrogen, or a C1-C4-alkyl group which is unsubstituted or substituted for example by halogen (F, Cl or Br) or by C1-C4-alkoxy (straight-chain and branched-chain), or both groups R5 and R6 can be linked, with the inclusion of the N atom, to form a heterocyclic 5- or 6-membered ring, such as the pyrrolidine ring or morpholine ring.

As a quaternary group, Y1 is for example one of the following groups:

wherein R1, R2 and R3 independently of one another are each a C1-C4-alkyl group which is unsubstituted or substituted by for example phenyl, OH, NH2, halogen (F, Cl or Br), CN, C1-C4-al koxy (straight-chain and branched-chain) or CONH2, or the groups R1 and R2 with the inclusion of the N atom can be linked together to form a heterocyclic 5- or 6-membered ring (for example a morpholine or pyrrolidine ring); or R1, R2 and R3 together with the N atom form a pyridinium ring which is unsubstituted or substituted by alkyl, OH, COOH, NH2 or CN; R4 is a hydrogen atom or a C1-C4-alkyl group (straightchain and branched-chain);R7 and R8 independently of one another are each a C1-C4-alkyl group which is unsubstituted or substituted by halogen (F, Cl or Br), OH or C1-C4-alkoxy (straight-chain or branchedchain), or the groups R7 and R8 with the inclusion of the N atom can be linked together to form a heterocyclic 5- or 6-membered ring (a morpholine or pyrrolidine ring);; R9 and R10 independently of one another are each hydrogen, or a C1-C4-alkyl group which is unsubstituted or substituted by for example halogen (F, Cl or Br), OH or C1-C4-alkoxy (straight-chain or branched-chain), or the groups R9 and R10 with the inclusion of the N atom can be linked together to form heterocyclic 5- or 6-membered ring, for example a morpholine or pyrrolidine ring; R1l is hydrogen, or a C1-C4-alkyl group which is unsubstituted or substituted by halogen (F, Cl or Br), OH or C1-C4-alkoxy (straight-chain or branchedchain); and R12, R13 and R14 independently of one another are each a C1-C4-alkyl group which is unsubstituted or substituted by halogen (F, Cl or Br), OH or C1-C4-alkoxy (straight-chain or branchedchain).

Both the Y and the Y1 group can be bound directly to the phenylene ring D, to the coupling component K or to the alkyl group X, or also to an external substituent bound to these groups, for example to an alkyl (C1-C4) group or to a group of the formula -CH2NHCO)-(alkyl-C1-C4.

As an anion, "An" denotes both organic and inorganic anions; for example: halogen, such as chloride, bromide or iodide ions, also sulfate, methylsulfate, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, phosphomolybdate, phosphotungstate, phosphotungstomolybdate, benzenesulfonate, naphthalenesulfonate, 4-chlorobenzenesulfonate, oxalate, maleinate, formiate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, methanesulfonate or benzoate ions, or complex anions, such as that of zinc chloride double salts.

Preferred anions "An" are the formiate, acetate, lactate, chloride, sulfate and phosphate ions.

The novel triazine compounds and mixtures of those of the formula I and/or la are yellow to blue compounds which can be produced in a known manner. They are symmetrical compounds, where for example the groups A, B and C, or just A and B, are identical, or asymmetrical compounds where the groups A, B and C differ from one another.

A process variant a) for producing a triazine compound according to the present invention comprises for example condensing cyanuric chloride or bromide of the formula IV

with an aminoazo compound of the formula V

or partially with various aminoazo compounds of the formula V and optionally an alkylamine of the formula VI NH2X (Vl), to obtain in the first case a compound of the formula VII and in the second case a compound of the formula Vlla

5 10 15 20 25 30 35 40 In the formulae V and VII, the symbols D, K and X have the meanings given under the formulae I and la.

If in the amino compounds of the formula V and VI the basic group Y and the cationic group Y,, respectively, are not present, these are subsequently introduced into the condensation products of the formulae VII and Villa, respectively.

The aminoazo compounds of the formula V are known, and can be produced in a known manner, just as can be the alkylamines of the formula VI.

A further production variant b) comprises condensing cyanuric chloride or bromide of the formula IV with a nitroamino compound or with an acylaminoaniline compound of the formula VIII

or partially with various nitro or NH-acyl compounds of the formula VIII and optionally an alkylamine of the formula VI; and subsequently reducing the condensation product, in the case where an NO2 group is present in the phenylene ring D, to the corresponding amino compound, or, in the case where an NHacyl group is bound to the phenylene ring D, saponifying the condensation product to the corresponding amino compound. There are thus produced the amino compounds of the formula IX and IXa

which are diazotised, and then coupled with a compound introducing the coupling component K to thus obtain the triazine compounds of the formulae I and la, respectively.When however in the starting compounds VIII and VI the basic group and the cationic group Y1, respectively, are not present, they are subsequently introduced into the products of the formulae VII and Vlla. This introduction is effected for example by condensing the compounds of the formulae VII and Vlla with an hydroxymethylchloroacetamide, and reacting the condensation product for example with pyridine or 3 dimethylamino-l -propylamine. Another possibility is to quaternise a quaternisable amino group present; for example, a dimethylaminopropyl group present can be quaternised with ethylene chlorohydrin.

The novel triazine compounds in both cases are then separated from the reaction medium and dried. If desired or if necessary, the anion An in the cationic compounds of the formula la can be exchanged for another anion in the known manner. It is however also possible to convert the novel triazine compounds, after concentrating the reaction medium by evaporation, directly into a liquid commercial form.

The novel triazine compounds, or mixtures thereof, of the formula(e) I and/or la are used in particular as dyes for dyeing and, with the addition of binders and optionally solvents, for printing materials dyeable with basic and cationic dyes, especially textile materials consisting for example advantageously of homo- or copolymers of acrylonitrile; or synthetic polyamides or polyesters which are modified by acid groups. Dyeing is preferably performed, in an aqueous, neutral or acid medium, by the exhaust process, optionally under pressure, or by the continuous process. The textile material can be in the most varied forms, for example in the form of fibres, filaments, fabrics, knitted goods, piece-goods and finished articles, such as shirts or pullovers.

Level yellow to blue dyeings and printings which are distinguished by very good general fastness properties, particularly by a very high degree of exhaustion and by good fastness to water, can be obtained by application of the dyes.

Furthermore, the novel triazine compounds of the formula I and/or la can be used also for dyeing and printing natural and regenerated cellulose materials, especially cotton and viscose, on which are likewise obtained deeply coloured yellow to blue dyeings.

The novel triazine compounds have on these textile materials good substantivity as well as a high degree of exhaustion, and the dyeings obtained have very good fastness properties, especially fastness to wet processing.

A further preferred use of the novel triazine compounds of the formulae I and la is the dyeing of paper of all types, in particular bleached, unsized and sized, lignin-free paper. These compounds are above all suitable for dyeing unsized paper (tissues) by virtue of their very high affinity for this substrate.

The novel triazine compounds of the formula(e) I and/or la are absorbed very well onto these substrates, the waste liquor being left colour!ess, a feature which constitutes a considerable ecological advantage, especially in view of the present-day effluent laws.

The resulting dyeings are fast to wet processing, that is to say, they exhibit no inclination to bleed when dyed paper in the wet condition is brought into contact with moist white paper. This property is particularly desirable with regard to so-called "tissues", in the case of which it is to be anticipated that the dyed paper in the wet state (for example soaked with water, alcohol, tensidesolution, and so forth ... ) will come into contact with other surfaces, such as textiles, paper, and the like, which have to be protected against soiling.

The good affinity for paper and the high rate of exhaustion of the novel dyes are of great advantage for the continuous dyeing of paper, and render possible a much wider application of this known economical process.

Finally, the novel triazine compounds can also be used for dyeing leather (by for example spraying, brushing and dipping), for preparing inks, and in the spinning-solution dyeing of polyacrylonitrile materials.

The invention is further illustrated by the following Examples but is not limited by them. The temperatures are given in degrees Centigrade, 'parts' are parts by weight and percentages are per cent by weight, whilst nm is the abbreviation for nanometer.

EXAMPLE 1 3.99 parts of 2,4,6-tris-3'-aminophenylamino-1 ,3,5-triazine are stirred up with 20 parts of glacial acetic acid and 12 parts by volume of concentrated hydrochloric acid. The suspension is diluted with 38 parts of water, and diazotised with 7.5 parts by volume of 4 N sodium nitrite solution at 0--5 OC. The diazo suspension is added to a solution of 7.2 parts of 3-pyridinium chloride-2,6-dihydroxy-4-methyl pyridine in 70 parts of water. The coupling mixture is made neutral to Congo red by the addition of sodium acetate solution. After completion of coupling, the dye is salted out by the addition of sodium chloride. The precipitated dye of the formula

is filtered off, washed with a 5% salt solution and dried. From an aqueous solution, the dye dyes paper pulp in yellow shades, and the waste liquor remaining is practically colourless.

EXAMPLE 2 3.99 parts of 2,4-bis-4'-aminophenylamino-6-3'-aminophenylamino- 1 ,3,5-triazine are diazotised in the manner given in Example 1. The diazo suspension is added to a solution of 7.9 parts of 2hydroxynaphthalene-3-carboxylic acid anilide in 250 parts of acetone, and, with the simultaneous dropwise addition of sodium hydroxide solution. the coupling mixture is maintained at pH 8. After coupling is completed, the product is filtered off, washed with water and dried.

12 parts of the product thus obtained are introduced at 0-50C into 120 parts by volume of sulfuric acid monohydrate and dissolved. 5.5 parts of hydroxymethylchloroacetamide are added, and the mixture is stirred at 0-50C for a further 20 hours, and is then poured into 1200 parts of ice and water.

The product which has precipitated is filtered off, washed neutral with water and dried. The dye is finely ground and is subsequently added to 100 parts of pyridine. The suspension obtained is heated at 1 000C for 1 hour, and is then cooled and filtered. The resulting dye of the formula

dyes paper pulp, from an aqueous acetic acid solution, in reddish-violet shades, and the waste liquor left is practically colourless.

EXAMPLE 3 3.99 parts of 2,4,6-tris-4'-aminophenylamino-1 3,5-triazine are diazotised as given in Example 1.

The diazo suspension is added to a solution of 6.3 parts of acetoacetic acid-o-anisidide in 80 parts of glycol monoethyl ether, and, with the simultaneous dropwise addition of sodium hydroxide solution, the coupling mixture is maintained at pH 8. After completion of coupling, the reaction product is filtered off, washed with water and dried.

10 parts of the product obtained above are introduced at 0--5 OC into 100 parts by volume of sulfuric acid monohydrate and dissolved. 5.5 parts of hydroxymethylchloroacetamide are added; the mixture is stirred at 0-50C for a further 20 hours, and is then poured into 1000 parts of ice and water.

The product which precipitates is filtered off, washed neutral with water and dried. The dye is finely ground and subsequently added to 50 parts of 3-dimethylamino-1-propylamine. The suspension is stirred for 4 hours at 55--600C, and afterwards the excess amine is distilled off in vacuo. The residue is stirred up with 10% sodium chloride solution and filtered off. The dye of the formula

dissolves in 2% aqueous acetic acid, and dyes paper pulp in greenish-yellow shades, the waste liquor left being virtually colourless.

EXAMPLE 4 3.99 parts of 2,4,6-tris-4'-aminophenylamino-1 ,3,5-triazine are diazotised as given in Example 1.

The diazo suspension is added to a solution of 7.1 parts of 1-dimethylamino-propyl-4-methyl-3-cyano- 6-hydroxy-2-pyridone in 100 parts of water. After coupling is completed, the pH value of the mixture is adjusted to 8 with sodium hydroxide solution. The product which has precipitated is filtered off, washed with water and dried.

2 parts of the product obtained above are stirred in 20 parts of ethylene chlorohydrin at 1 200C for 3 hours, and the excess ethylene chlorohydrin is subsequently distilled off in vacuo. The residue dissolves in water to form a red solution, and dyes paper pulp in brownish red shades, after which the waster liquor is practically colourless. The dye corresponds to the formula

EXAMPLE 5 3.99 parts of 2,4,6-tris-4'-aminophenylamino-1 ,3,5-triazine are diazotised as given in Example 1.

The diazo suspension is added to a solution of 5.2 parts of 5-aminomethyl-2-naphthylamine in 100 parts of 5% hydrochloric acid. The reaction mixture is stirred at room temperature until coupling is completed, and is subsequently neutralised with sodium hydroxide solution. The dye which precipitates is filtered off, washed with water and dried. It corresponds to the formula

From an aqueous/acetic acid solution, the above dye dyes paper pulp in brown shades, and the waste liquor is left colourless.

EXAMPLE 6 9.2 parts of cyanuric chloride, 36 parts of 4-amino-2'-hydroxy-5'-methylazobenzene and 400 parts of anhydrous nitrobenzene are slowly heated to 1 600C, and stirring is maintained at this temperature for 1 5 hours. After cooling, the suspension is filtered off, washed with alcohol and dried.

7.5 parts of the product obtained above are introduced at 0--5 OC into 70 parts by volume of sulfuric acid monohydrate and dissolved. 3.7 parts of hydroxymethylchloroacetamide are added; the mixture is stirred at O-50C for a further 20 hours, and is then poured into 700 parts of ice and water.

The product which has precipitated is filtered off, washed neutral with water and dried. The dye is finely ground, and subsequently added to 40 parts of 3-dimethylaminopropylamine. The suspension is stirred at 50-550C for 2 hours, and the excess amine is then distilled off in vacuo. The residue is dissolved hot in 2% acetic acid, and, after filtration of the solution, the dye is salted out of the filtrate. The precipitated dye of the formula

is filtered off and dried. It dyes paper pulp in yellow shades and leaves the waste liquor practically colourless.

Further dyes are obtained by applying the procedure of the respective Example given in column Ill of the following Tables I to IV, but using ( nalogously the products shown in column I of the same Tables. The resulting dyes of the given formulae produce on paper the shades of colour listed in column II.

TABLE I

Ex. 1 II III R R R Position of K' V1 V2 7 H H H 4 8 15 -C2H3 # yellow 1 8 H H 14-CH3 3 9 18 H # yellow 1 9 H H 14-Cl 4 10 16 -C3H6N(CH2)3 # brown 1 10 2-OCH3 8-OCH3 14-OC2H5 4 10 16 -C3H4N(CH2)5# -CN red-brown 1 11 H H 15-SO2CH3 3 9 16 -C3H4N(CH3)2 -CN goiden 5 yellow TABLE I (Continued)

Ex I II III R R R Position of K' V1 V2 12 H H 15-NO2 3 9 16 # -CN brown 4 13 H 8-Br H 3 10 16 # -CONH2 brown 1 14 H H H 4 10 16 -C2H5 # orange 2 15 8-OCH2 H H 3 9 15 -H # yellow 2 16 2-OCH3 2-OCH3 2-OCH2 4 10 18 -C2H5 # red 2 TABLE II

Ex. I II III R R R Position V3 V4 V5 V6 V7 of K'' 17 H H H 4 10 16 CH3 CH H H # golden 1 yellow 18 6-OCH2 H H 3 9 15 CH2 CH H # H yellow 1 19 H H H 4 70 16 CH2 CH C2H5 H # golden yellow 2 20 2-OCH3 8-OCH3 14-OCH3 4 10 16 # OH H H H orange 1 21 H H 14-CH2 4 10 16 H NH2 H # # yellow 2 22 H H 14-Cl 4 10 16 CH2 NH2 H # # yellow 2 TABLE III

Ex. I II III 23 H H 14-Cl 4 10 16 # golden- 2 yellow 24 H H 14-CH2 4 10 16 # yellow 1 25 H 8-Br H 3 10 16 # scartet 1 TABLE III (Continued)

Ex. I II III R R R Position of K''' K''' 26 H 12-OCH3 H 4 9 18 # brown 1 27 H H H 4 10 16 # orange 1 28 H H H 4 10 16 # red 1 TABLE III (Continued)

Ex I II III R R R Position of K''' K''' 29 H H H 4 10 16 # violet 5 30 H H H 3 9 16 # orange 2 31 H H H 3 9 16 # yellow 1 TABLE III (Continued)

Ex. I II III R R R Position of K''' K''' 32 H H H 4 10 16 # yellow 5 33 H H H 4 10 16 # yellow 2 34 H H H 4 10 16 # reddish- 5 brown TABLE IV

Ex. I II III R R R Position of K''' K''' 35 -NHC2H5N(CH5)2 4 10 # brown 1 36 -NHC3H6N(CH3)3CH3SO4# 3 9 # yellow 1 37 2-CH2 8-CH2 -NHC2H5 4 10 # scarlet 5 TABLE IV (Continued)

Ex. I II III R R R Posltion of K''' K''' 38 2-Cl 8-Cl -NHC2H4OH 4 10 # raddlsh- 1 brown 39 H H -NHC3H6OCH3 4 10 # orange 1 40 2-CH3 8-CH3 -NHC2H4NHCOCH3 4 10 # yallow 2 TABLE IV (Continued)

Ex I II III R R R Position of K''' K''' 41 6-OCH3 12-OCH3 -NHC4H9 3 9 # scarlet 2 42 H H -NHC2H4Cl 3 9 # red 5 EXAMPLE 43 50 parts of chemically bleached beechwood sulfite are mixed together with 50 parts of bleached RKN 1 5 (freeness value 220 SR) and 2 parts of the dye according to Example 1 in water (pH 6, water hardness 100 dH, temperature 200C, ratio of goods to liquor 1:40). After 1 5 minutes' stirring, paper sheets are produced on a Frank sheet-former.

The paper is dyed in a very intense yellow shade, and the waste liquor is completely colourless.

The degree of exhaustion attained is practically 100%, and the dyeing has excellent fastness to wet processing.

EXAMPLE 44 A paper web of bleached beechwood sulfite (220 SR) is produced on a continuously operating laboratory paper-making machine. Ten seconds before entry into the breast box, an aqueous soluton of the dye according to Example 1 is continuously fed in measured amounts, with vigorous turbulence, into the diluted paper pulp (0.5% dyeing, ratio of goods to liquor 1:400, water hardness 100 dH, pH 6, temperature 200C).

A deeply coloured yellow shade of medium intensity is produced on the paper web, and the waste liquor is left completely colourless.

EXAMPLE 45 10 parts of cotton fabric (bleached, mercerised cotton) are dyed, on a laboratory beam-dyeing machine, in 200 parts of a liquor (water hardness 100 dH, pH 4, 3 circulations of the dye liquor per minute) containing 0.05 part of the dye according to Example 1. The temperature is raised in 60 minutes from 200 to 1 000C, and then maintained constant for 1 5 minutes.

The dye liquor is completely exhuasted, and there is produced on the cotton fabric a deeply coloured yellow dyeing which is distinguished by good fastness to light and by very good fastness to wet processing.

When a textile fabric made from regenerated cellulose (viscose) is dyed using the procedure described above, there is obtained on this material, with the dye of Example 1, a deeply coloured yellow dyeing having good fastness to light and very good fastness to wet processing.

Claims

1. A triazine compound of the formula I or la

or a mixture thereof, wherein A, B and C independently of one another are each a group of the formula II

or one of the groups A, B or C is a group of the formula Ill -NHX (III) and the other two independently of one another correspond to the formula II, in which formulae, the phenylene group D can be substituted, K is any chosen coupling component, X is an unsubstituted or substituted C1-C5-alkyl group, Yls a basic group, and Y1 is a quaternary group, n is the number 2, 3 or 4, and An is any given anion.

2. A triazine compound of the formula la according to Claim 1.

3. A triazine compound of the formula(e) I and/or la according to Claims 1 and 2, wherein all three groups A, B and C are identical.

4. A triazine compound of the formula(e) I and/or la according to any preceding claim, wherein the coupling component K in the formula II is acetoacetic acid anilide, phenol, pyridone, quinolone, pyrazolone, aminopyrazole, indole, aniline, aminopyridine, naphthol, naphthocarboxylic acid anilide, naphthylamine, aminothiazole or thiophene.

5. A triazine compound according to any preceding claim, wherein the phenylene group D in the formula II is substituted by: alkyl(C1-C4), alkoxy(C1-C4), halogen, NO2, CN or S02-alkyl(C1-C4).

6. A triazine compound according to any preceding claim, wherein the alkyl group X in the formula Ill is substituted by: OH, halogen, alkoxy(C1-C4) or acylamino.

7. A triazine compound of the formula I according to any preceding claim, wherein the basic group Y is the group

wherein R5 and R6 independently of one another are each hydrogen or unsubstituted or substituted alkyl(C1-C4), or both R5 and R6 with the inclusion of the N atom can be linked to form a heterocyclic 5- or 6membered ring.

8. A triazine compound of the formula la according to any preceding claim, wherein the quaternary group Y1 is one of the following groups:

wherein R1, R2 and R2 independently of one another are each an unsubstituted or substituted C1-C4- alkyl group, or the groups R, and R2 or R1, R2 and R3 with the inclusion of the N atom can be linked to form a heterocyclic 5- or 6-membered ring, R4 is a hydrogen atom or a C1-C4-alkyl group, R7 and R8 independently of one another are each an unsubstituted or substituted C1-C4-alkyl group, or R7 and R8 with the inclusion of the n atom can be linked to form a heterocyclic 5- or 6-membered ring, R9 and R10 independently of one another are each hydrogen, or an unsubstituted or substituted C1-C4-alkyl group, or R9 and R10 with the inclusion of the N atom can be linked together to form a heterocyclic 5- or 6membered ring, R11 is hydrogen, or an unsubstituted or substituted C1-C4-alkyl group, and R12, R13 and R,4 independently of one another are each an unsubstituted or substituted C1-C4-alkyl group.

9. A process for producing a triazine compounds of the formulae I and la, or mixtures thereof, according to Claim 1, which process comprises a) condensing a cyanuric chloride or bromide of the formula IV

with an aminoazo compound of the formula V

or partially with various aminoazo compounds of the formula V and optionally an alkylamine of the formula VI NH2X (Vl) to obtain in the first case a compound of the formula VII and in the second case a compound of the formula Vlla

in which formulae, the symbols D, K and X have the meanings defined under the formulae I and la according to Claim 1, and if in the amino compounds of the formulae V and VI the basic group Y and the cationic group Y1, respectively, are not present, these are subsequently introduced into the condensation products of the formulae VII and Vlla, respectively; or b) condensing a cyanuric chloride or bromide of the formula IV with a nitroamino compound or with an acylaminoaniline compound of the formula VIII

or partially with various nitro and NH-acyl compounds of the formula VIII and optionally an alkylamine of the formula Vl; and subsequently reducing the condensation product, in the case where an NO2 group is present in the phenylene ring D, to the corresponding amino compound, or, in the case where an NHacyl group is bound to the phenylene ring D, saponifying the condensation product to the corresponding amino compound, to thus obtain amino compounds of the formulae IX and IXa, respectively::

diazotising the resulting compounds, and coupling the diazotised product with a compound introducing the coupling component K, by which procedure are obtained the triazine compounds of the formulae I and la, whereby, in the case where in the starting compounds VIII and VI the basic group Y and the cationic group Y1, respectively, are not present, these are subsequently introduced into the products of the formulae VII and Vlla, respectively.

10. The use of the triazine compounds, or mixtures thereof, of the formulae I and la according to Claim 1, or of the triazine compounds obtained according to Claim 9, as dyes for dyeing and printing textile materials, leather and paper of all types.

1 The use according to Claim 10 for dyeing and printing polyacrylonitrile materials, acid modified polyester or polyamide materials, and natural and regenerated cellulose materials.

12. The use according to Claim 11 for dyeing and printing lignin-free, bleached and unsized paper.

13. The materials treated and dyed or printed with the triazine compounds of the formulae I and la according to Claim 1.

14. A triazine compound of the formula I or la according to Claim 1 substantially as hereinbefore described with reference to any one of the foregoing Examples.

15. A process according to Claim 9 substantially as hereinbefore described with reference to any one of Examples 1 to 42.

1 6. The use according to Claim 10 substantially as hereinbefore described with reference to any one of Examples 43 to 45.